Process for the manufacture of granular detergent compositions comprising nonionic surfactant

ABSTRACT

PCT No. PCT/US96/00527 Sec. 371 Date Sep. 24, 1997 Sec. 102(e) Date Sep. 24, 1997 PCT Filed Jan. 5, 1996 PCT Pub. No. WO96/23048 PCT Pub. Date Aug. 1, 1996A process for the manufacture of detergent compositions from a surfactant paste which is substantially in the solid phase at temperatures of 25 DEG  C. and below comprises the steps of: (i) mixing the surfactant paste at a temperature above its softening point, the surfactant paste comprising at least 50% by weight of nonionic surfactant; (ii) forming the molten surfactant paste into drops on a cooling surface; (iii) forming solid pastilles by cooling the drops of molten surfactant paste; and (iv) removing solidified pastilles from the cooling surface.

The present invention relates to a process for the manufacture ofdetergent compositions or components from a surfactant paste which isrich in nonionic surfactant.

Nonionic surfactants are important components of current laundrydetergent compositions. Present trends demand particulate components orcompositions which have a high level of nonionic surfactant.

WO9206160, published on 16th Apr. 1992, discloses high performingnonionic surfactant systems based on mixtures of glucose amides andethoxylated nonionic surfactants. In one example (example 20) acomponent is described which comprises a nonionic surfactant systemwhich is a mixture of ethoxylated nonionic and N-methyl glucose amide inaqueous solution. The surfactant system is granulated in a high shearmixer in the presence of anionic surfactants and detergent powders. Thetotal nonionic surfactant concentration of the finished granulardetergent component is 26% by weight, and the anionic surfactantconcentration is 21% by weight.

EP-A-643 130, published on Mar. 15, 1995, describes a granular laundrydetergent having good physical characteristics, which delivers nonionicsurfactants which have been selected for high performance in to thewash. Surfactant pastes are described which have a defined viscosityprofile which enables high shear mixing and granulation processes to beperformed in order to make granular detergent components having nonionicsurfactant activities in excess of 50% by weight (in Example 9).

The present invention aims to provide a new and versatile process for aneven wider range of nonionic surfactant rich pastes. This is achievedby:

(i) mixing the surfactant paste at a temperature above its softeningpoint, the surfactant paste comprising at least 50% by weight ofnonionic surfactants;

(ii) forming the molten surfactant paste into drops on a coolingsurface;

(iii) forming pastilles by cooling and solidifying the drops of moltensurfactant paste;

(iv) removing solidified pastilles from the cooling surface.

The process of the invention provides granular detergent componentshaving nonionic surfactant activities in excess of 50% by weight whichdeliver high performing nonionic surfactants to the wash. The processplaces still fewer restrictions on the viscosity characteristics ofsurfactant pastes that are suitable for processing into granulardetergent components than the processes of the prior art.

SUMMARY OF THE INVENTION

The invention relates to a process for the manufacture of detergentcompositions or components from a surfactant paste which issubstantially in the solid phase at temperatures of 25° C. and below,comprising the steps of:

(i) mixing the surfactant paste at a temperature above its softeningpoint, the surfactant paste comprising at least 50% by weight ofnonionic surfactant;

(ii) forming the molten surfactant paste into drops on a coolingsurface;

(iii) forming solid pastilles by cooling the drops of molten surfactantpaste; and

(iv) removing solidified pastilles from the cooling surface.

In a preferred embodiment of the invention the surfactant paste furthercomprises anionic surfactant. In this embodiment the surfactant pastepreferably comprises anionic surfactant and nonionic surfactant in aratio of from 1:100 to 1:1, and furthermore, preferably has a watercomponent of less than 15%, more preferably less than 10% by weight ofthe surfactant paste.

Suitable nonionic surfactants may be selected from the group consistingof ethoxylated nonionic surfactants, glycerol ethers, glucosamides,glycerol amides, glycerol esters, fatty acids, fatty acid esters, fattyamides, alkyl polyglucosides, alkyl polyglycol ethers, polyethyleneglycols, ethoxylated alkyl phenols and mixtures thereof.

In particular a surfactant system comprising a mixture of polyhydroxyfatty acid amide and an ethoxylated nonionic surfactant in the ratio offrom 3:7 to 7:3 is preferred.

In a particular embodiment of the invention, the molten surfactant pasteis formed into drops by a continuous rotary drop former comprising outerand inner coaxial cylinders, both cylinders comprising a series ofopenings, at least one of the cylinders being rotatable. The moltensurfactant drops are conveniently formed on a continuous steel coolingbelt and, optionally, cooled by spraying a cooling liquid on to theopposite side of the belt to the side on which the drops are formed.

In a further aspect, the invention relates to granular detergentcomponents or compositions comprising pastilles, the pastillescomprising at least 50% by weight of nonionic surfactant,characteristically have a generally rounded surface profile and at leastone substantially planar surface.

An advantage of the process of the present invention is that thefinished particles or "(micro)pastilles" have a very uniform and narrowparticle size distribution and are substantially dust-free.

DETAILED DESCRIPTION OF THE INVENTION

The process defined herein is a "pastillation" or "micropastillation"process. "Pastilles" or "micropastilles" of granular laundry detergentcomponents (or finished granular laundry detergent compositions) areformed by the solidification of molten droplets. A known drop formingdevice is described in DE 28 53 054, published on 12th Jun. 1980, ownedby Sandvik Conveyor GmbH of Fellbach, Germany. The known device is arotary drop former comprising outer and inner coaxial cylinders, theouter cylinder being rotatable, and the inner cylinder being stationary.The outer cylinder is perforated over its entire circumference, andthose perforations periodically become aligned with a series of openings(or with a slit or a nozzle lip) formed in the inner cylinder. The meltcontained inside the inner cylinder drips under pressure through thealigned openings.

In the known device, drops of the melt are formed directly onto acooling belt to form on the belt a row of drops distributed adjacent toeach other across the width of the belt. The drops thus formed on thecooling belt crystallise into solid pellets, or "(micro)pastilles".

It is preferred that the cooling belt is a continuous stainless steelconveyor belt. Most conveniently the cooling belt is cooled by sprayinga cooling liquid on to the side of the belt opposite that on whichdroplets are formed. This enables any direct contact between thesurfactant paste and the cooling liquid to be avoided.

After the "(micro)pastilles" are solidified they are removed from thebelt, optionally with the aid of a scraper blade. Pastilles made by theprocess of the invention are generally recognisable by their surfaceprofile which is generally round, but has a planar surface. The planarsurface corresponds to the area of the pastille that has been in directcontact with the cooling belt.

In an alternative embodiment of the present invention the moltendroplets may be formed and cooled on a rotating cooling drum, or on asurface such as a rotating disc. A suitable device is a Disc Pastillatorfor uniform free flowing pastilles manufactured by GoudscheMaschinefabriek B. V. of Waddinxveen, The Netherlands. Another device isdescribed in their Dutch patent application NL-A-7 113 934.

In all of these devices outer surface of the droplet former and thecooling surface will normally move at the same linear speed so thatsubstantially round uniform droplets are formed. However non-uniformdroplets may be formed by driving the outer surface of the dropletformer and the cooling surface at different linear speeds.

By cooling surface it is meant herein that the surface of the belt,drum, or disc is cooled by a cooling fluid such as water or air. Thecooling fluid may be applied to the opposite surface of the belt, drumor disc to the surface on which the droplets are formed; on the coolingfluid may be applied to the same side as that on which the droplets areformed; or both surfaces at the same time.

In a further embodiment of the process, the cooling surface mayoptionally be heated locally in the region of the droplet formation.This improves the adhesiveness of the product to the belt.

The surfactant paste of the present invention may have a wide range ofcompositions as a result of the flexibility of the process of theinvention. Suitable surfactant paste components are described below:

The term "surfactant paste" as used herein means a mixture of one ormore surfactants comprising nonionic surfactants alone or a mixedanionic/nonionic surfactant system. Whilst other components such aswater and solvents (e.g. short chain alcohols) may be present in thesurfactant system, these will generally be minimised and preferablyexcluded.

The term "viscosity" as used herein means the viscosity measured at ashear rate of 25 s⁻¹. The viscosity can be measured by rotationalanalysis (e.g. a rheometer). Suitable instruments for these measurementsare manufactured by Physica Messtechnik, Germany, (supplied by ThermoInstrument Systems of Breda, Netherlands).

The term "high active" as used herein refers to nonionic surfactantactivities of at least 50%, preferably at least 60% by weight.

Surfactant Pastes

While any nonionic surfactant may be usefully employed in the presentinvention, two families of nonionics have been found to be particularlyuseful. These are nonionic surfactants based on alkoxylated (especiallyethoxylated) alcohols, and those nonionic surfactants based on amidationproducts of fatty acid esters and N-alkyl polyhydroxy amine. Theamidation products of the esters and the amines are generally referredto herein as polyhydroxy fatty acid amides. Particularly useful in thepresent invention are mixtures comprising two or more nonionicsurfactacts wherein at least one nonionic surfactant is selected fromeach of the groups of alkoxylated alcohols and the polyhydroxy fattyacid amides.

Suitable nonionic surfactants include compounds produced by thecondensation of alkylene oxide groups (hydrophilic in nature) with anorganic hydrophobic compound, which may be aliphatic or alkyl aromaticin nature. The length of the polyoxyalkylene group which is condensedwith any particular hydrophobic group can be readily adjusted to yield awater-soluble compound having the desired degree of balance betweenhydrophilic and hydrophobic elements.

Particularly preferred for use in the present invention are nonionicsurfactants such as the polyethylene oxide condensates of alkyl phenols,e.g., the condensation products of alkyl phenols having an alkyl groupcontaining from about 6 to 16 carbon atoms, in either a straight chainor branched chain configuration, with from about 4 to 25 moles ofethylene oxide per mole of alkyl phenol.

Preferred nonionics are the water-soluble condensation products ofaliphatic alcohols containing from 8 to 22 carbon atoms, in eitherstraight chain or branched configuration, with an average of up to 25moles of ethylene oxide per more of alcohol. Particularly preferred arethe condensation products of alcohols having an alkyl group containingfrom about 9 to 15 carbon atoms with from about 2 to 10 moles ofethylene oxide per mole of alcohol; and condensation products ofpropylene glycol with ethylene oxide. Most preferred are condensationproducts of alcohols having an alkyl group containing from about 12 to15 carbon atoms with an average of about 3 moles of ethylene oxide permole of alcohol.

It is a particularly preferred embodiment of the present invention thatthe nonionic surfactant paste also includes a polyhydroxy fatty acidamide component.

Polyhydroxy fatty acid amides may be produced by reacting a fatty acidester and an N-alkyl polyhydroxy amine. The preferred amine for use inthe present invention is N--(R1)-CH2(CH2OH)4-CH2-OH, where R1 istypically a alkyl, e.g. methyl group; and the preferred ester is aC12-C20 fatty acid methyl ester.

Methods of manufacturing polyhydroxy fatty acid amides have beendescribed in WO 92 6073, published on 16th Apr. 1992. This applicationdescribes the preparation of polyhydroxy fatty acid amides in thepresence of solvents. In a highly preferred embodiment of the inventionN-methyl glucamine is reacted with a C12-C20 methyl ester. It also saysthat the formulator of granular detergent compositions may find itconvenient to run the amidation reaction in the presence of solventswhich comprise alkoxylated, especially ethoxylated (EO 3-8) C12-C14alcohols (page 15, lines 22-27). This can directly yield nonionicsurfactant pastes which are preferred in the present invention, such asthose comprising N-methyl glucosamide and C12-C14 alcohols with anaverage of 3 ethoxylate groups per molecule.

Nonionic surfactant pastes, and granular detergents made from suchpastes have been described in WO 92 6160, published on 16th Apr. 1992.

Both of these patent applications describe nonionic surfactant pastestogether with suitable manufacturing processes for their synthesis,which have been found to be suitable for use in the present invention.However, for the purposes of the present invention is necessary tominimise (and preferably exclude) the presence of water (or othersolvents).

The surfactant paste may also comprise anionic surfactants, indeed theinclusion of such surfactants may be of considerable advantage in orderto improve the rate of solubility of the granular surfactant.

Anionic Surfactants

Nonlimiting examples of anionic surfactants useful herein include theconventional C₁₁ -C₁₈ alkyl benzene sulfonates ("LAS") and primary,branched-chain and random C₁₀ -C₂₀ alkyl sulfates ("AS"), the C₁₀ -C₁₈secondary (2,3) alkyl sulfates of the formula CH₃ (CH₂)_(x) (CHOSO₃₋M⁺)CH₃ and CH₃ (CH₂)_(y) (CHOSO₃₋ M⁺) CH₂ CH₃ where x and (y+1) areintegers of at least about 7, preferably at least about 9, and M is awater-solubilizing cation, especially sodium, unsaturated sulfates suchas oleyl sulfate, the C₁₀ -C₁₈ alkyl alkoxy sulfates ("AE_(x) S";especially EO 1-7 ethoxy sulfates), C₁₀ -C₁₈ alkyl alkoxy carboxylates(especially the EO 1-5 ethoxycarboxylates), the C₁₀₋₁₈ glycerol ethers,the C₁₀ -C₁₈ alkyl polyglycosides and their corresponding sulfatedpolyglycosides, the C₁₂ -C₁₈ alpha-sulfonated fatty acid esters methylester sulphonate (MES), and oleoyl sarcosinates.

Other Surfactants

The laundry detergent compositions of the present invention may alsocontain cationic, ampholytic, zwitterionic, and semi-polar surfactants.

Cationic detersive surfactants suitable for use in the laundry detergentcompositions of the present invention are those having one long-chainhydrocarbyl group. Examples of such cationic surfactants include theammonium surfactants such as alkyldimethylammonium halogenides, andthose surfactants having the formula:

     R.sup.2 (OR.sup.3)y! R.sup.4 (OR.sup.3)y!.sub.2 R.sup.5 N+X--

wherein R2 is an alkyl or alkyl benzyl group having from about 8 toabout 18 carbon atoms in the alkyl chain, each R³ is selected from thegroup consisting of --CH₂ CH₂ --, --CH₂ CH(CH₃)--, --CH₂ CH(CH₂ OH)--,--CH₂ CH₂ CH₂ --, and mixtures thereof; each R⁴ is selected from thegroup consisting of C₁ -C₄ alkyl, C₁ -C₄ hydroxyalkyl, benzyl ringstructures formed by joining the two R⁴ groups, --CH₂ COH--CHOHCOR⁶CHOHCH₂ OH wherein R⁶ is any hexose or hexose polymer having a molecularweight less than about 1000, and hydrogen when y is not 0; R⁵ is thesame as R⁴ or is an alkyl chain wherein the total number of carbon atomsof R² plus R⁵ is not more than about 18; each y is from 0 to about 10and the sum of the y values is from 0 to about 15; and X is anycompatible anion.

Other cationic surfactants useful herein are also described in U.S. Pat.No. 4,228,044, Cambre, issued Oct. 14, 1980, incorporated herein byreference.

When included therein, the laundry detergent compositions of the presentinvention typically comprise from 0% to about 25%, preferably form about3% to about 15% by weight of such cationic surfactants.

Ampholytic surfactants are also suitable for use in the laundrydetergent compositions of the present invention. These surfactants canbe broadly described as aliphatic derivatives of secondary or tertiaryamines, or aliphatic derivatives of heterocyclic secondary and tertiaryamines in which the aliphatic radical can be straight- or branchedchain. One of the aliphatic substituents contains at least 8 carbonatoms, typically from about 8 to about 18 carbon atoms, and at least onecontains an anionic water-solubilizing group e.g. carboxy, sulfonate,sulfate. See U.S. Pat. No. 3,929,678 to Laughlin et al., issued Dec. 30,1975 at column 19, lines 18-35 (herein incorporated by reference) forexamples of ampholytic surfactants.

When included therein, the laundry detergent compositions of the presentinvention typically comprise form 0% to about 15%, preferably from about1% to about 10% by weight of such ampholytic surfactants.

Zwitterionic surfactants are also suitable for use in laundry detergentcompositions. These surfactants can be broadly described as derivativesof secondary and tertiary amines, derivates of heterocyclic secondaryand tertiary amines, or derivatives of quaternary ammonium, quarternaryphosphonium or tertiary sulfonium compounds. See U.S. Pat. No. 3,929,678to Laughlin et al., issued Dec. 30, 1975 at columns 19, line 38 throughcolumn 22, line 48 (herein incorporated by reference) for examples ofzwitterionic surfactants.

When included therein, the laundry detergent compositions of the presentinvention typically comprise form 0% to about 15%, preferably from about1% to about 10% by weight of such zwitterionic surfactants.

Semi-polar nonionic surfactants are a special category of nonionicsurfactants which include water-soluble amine oxides containing onealkyl moiety of from about 10 to about 18 carbon atoms and 2 moietiesselected from the group consisting af alkyl groups and hydrocyalkylgroups containing form about 1 to about 3 carbon atoms; water-solublephosphine oxides containing one alkyl moiety of form about 10 to about18 carbon atoms and 2 moieties selected form the group consisting ofalkyl groups and hydroxyalkyl groups containing from about 1 to about 3carbon atoms.

Semi-polar nonionic detergent surfactants include the amine oxidesurfactants having the formula: ##STR1## wherein R³ is an alkyl,hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing fromabout 8 to about 22 carbon atoms; R⁴ is an alkylene or hydroxyalkylenegroup containing from about 2 to about 3 carbon atoms or mixturesthereof; x is form 0 to about 3; and each R⁵ is an alkyl or hydroxyalkylgroup containing form about 1 to about 3 carbon atoms or a polyethyleneoxide group containing from about 1 to about 3 ethylene oxide groups.The R⁵ groups can be attached to each other, e.g., through an oxygen ornitrogen atom, to form a ring structure.

There amine oxide surfactants in particular include C₁₀ -C₁₈ alkyldimenthyl amine oxides and C₈ -C₁₂ alkoxy ethyl dihydroxy ethyl amineoxides.

When included therein, the laundry detergent compositions of the presentinvention typically comprise form 0% to about 15%, preferably from about1% to about 10% by weight of such semi-polar nonionic surfactants.

Bleaching Compounds--Bleaching Agents and Bleach Activators

The detergent compositions herein may optionally contain bleachingagents or bleaching compositions containing a bleaching agent and one ormore bleach activators. When present, bleaching agents will typically beat levels of from about 1% to about 30%, more typically from about 5% toabout 20%, of the detergent composition, especially for fabriclaundering. If present, the amount of bleach activators will typicallybe from about 0.1% to about 60%, more typically from about 0.5% to about40% of the bleaching composition comprising the bleachingagent-plus-bleach activator.

The bleaching agents used herein can be any of the bleaching agentsuseful for detergent compositions in textile cleaning. These includeoxygen bleaches as well as other bleaching agents. Perborate bleaches,e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be usedherein.

Another category of bleaching agent that can be used without restrictionencompasses percarboxylic acid bleaching agents and salts thereof.Suitable examples of this class of agents include magnesiummonoperoxyphthalate hexahydrate, the magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid anddiperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S.Pat. No. 4,483,781, Hartman, issued Nov. 20, 1984, U.S. patentapplication Ser. No. 740,446, Burns et al, filed Jun. 3, 1985, EuropeanPatent Application 0,133,354, Banks et al, published Feb. 20, 1985, andU.S. Pat. No. 4,412,934, Chung et al, issued Nov. 1, 1983. Highlypreferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproicacid as described in U.S. Pat. No. 4,634,551, issued Jan. 6, 1987 toBurns et al.

Peroxygen bleaching agents can also be used. Suitable peroxygenbleaching compounds include sodium carbonate peroxyhydrate andequivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate,urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE,manufactured commercially by DuPont) can also be used.

A preferred percarbonate bleach comprises dry particles having anaverage particle size in the range from about 500 micrometers to about1,000 micrometers, not more than about 10% by weight of said particlesbeing smaller than about 200 micrometers and not more than about 10% byweight of said particles being larger than about 1,250 micrometers.Optionally, the percarbonate can be coated with silicate, borate orwater-soluble surfactants. Percarbonate is available from variouscommercial sources such as FMC, Solvay and Tokai Denka.

Mixtures of bleaching agents can also be used.

Peroxygen bleaching agents, the perborates, the percarbonates, etc., arepreferably combined with bleach activators, which lead to the in situproduction in aqueous solution (i.e., during the washing process) of theperoxy acid corresponding to the bleach activator. Various nonlimitingexamples of activators are disclosed in U.S. Pat. No. 4,915,854, issuedApr. 10, 1990 to Mao et al, and U.S. Pat. No. 4,412,934. Thenonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine(TAED) activators are typical, and mixtures thereof can also be used.See also U.S. Pat. No. 4,634,551 for other typical bleaches andactivators useful herein.

Highly preferred amido-derived bleach activators are those of theformulae:

    R.sup.1 N(R.sup.5)C(O)R.sup.2 C(O)L or R.sup.1 C(O)N(R.sup.5)R.sup.2 C(O)L

wherein R¹ is an alkyl group containing from about 6 to about 12 carbonatoms, R² is an alkylene containing from 1 to about 6 carbon atoms, R⁵is H or alkyl, aryl, or alkaryl containing from about 1 to about 10carbon atoms, and L is any suitable leaving group. A leaving group isany group that is displaced from the bleach activator as a consequenceof the nucleophilic attack on the bleach activator by the perhydrolysisanion. A preferred leaving group is phenyl sulfonate.

Preferred examples of bleach activators of the above formulae include(6-octanamidocaproyl)oxybenzenesulfonate,(6-nonanamidocaproyl)oxybenzenesulfonate,(6-decanamidocaproyl)oxybenzenesulfonate, and mixtures thereof asdescribed in U.S. Pat. No. 4,634,551, incorporated herein by reference.

Another class of bleach activators comprises the benzoxazin-typeactivators disclosed by Hodge et al in U.S. Pat. No. 4,966,723, issuedOct. 30, 1990, incorporated herein by reference. A highly preferredactivator of the benzoxazin-type is: ##STR2##

Still another class of preferred bleach activators includes the acyllactam activators, especially acyl caprolactams and acyl valerolactamsof the formulae: ##STR3## wherein R⁶ is H or an alkyl, aryl, alkoxyaryl,or alkaryl group containing from 1 to about 12 carbon atoms. Highlypreferred lactam activators include benzoyl caprolactam, octanoylcaprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam,decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam,octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam,nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixturesthereof. See also U.S. Pat. No. 4,545,784, issued to Sanderson, Oct. 8,1985, incorporated herein by reference, which discloses acylcaprolactams, including benzoyl caprolactam, adsorbed into sodiumperborate.

Bleaching agents other than oxygen bleaching agents are also known inthe art and can be utilized herein. One type of non-oxygen bleachingagent of particular interest includes photoactivated bleaching agentssuch as the sulfonated zinc and/or aluminum phthalocyanines. See U.S.Pat. No. 4,033,718, issued Jul. 5, 1977 to Holcombe et al. If used,detergent compositions will typically contain from about 0.025% to about1.25%, by weight, of such bleaches, especially sulfonate zincphthalocyanine.

If desired, the bleaching compounds can be catalyzed by means of amanganese compound. Such compounds are well known in the art andinclude, for example, the manganese-based catalysts disclosed in U.S.Pat. No. 5,246,621, U.S. Pat. No. 5,244,594; U.S. Pat. No. 5,194,416;U.S. Pat. No. 5,114,606; and European Pat. App. Pub. Nos. 549,271A1,549,272A1, 544,440A2, and 544,490A1; Preferred examples of thesecatalysts include Mn^(IV) ₂ (u-O)₃(1,4,7-trimethyl-1,4,7-triazacyclononane)₂ (PF₆)₂, Mn^(III) ₂ (u-O)₁(u-OAc)₂ (1,4,7-trimethyl-1,4,7-triazacyclononane)₂ -(ClO₄)₂, Mn^(IV) ₄(u-O)₆ (1,4,7-triazacyclononane)₄ (ClO₄)₄, Mn^(III) Mn^(IV) ₄ (u-O)₁(u-OAc)₂ -(1,4,7-trimethyl-1,4,7-triazacyclononane)₂ (ClO₄)₃, Mn^(IV)-(1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH₃)₃ (PF₆), and mixturesthereof. Other metal-based bleach catalysts include those disclosed inU.S. Pat. No. 4,430,243 and U.S. Pat. No. 5,114,611. The use ofmanganese with various complex ligands to enhance bleaching is alsoreported in the following United States Patents: U.S. Pat. Nos.4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147;5,153,161; and 5,227,084.

Detergent builders/powders

Inorganic or P-containing detergent builders include, but are notlimited to, the alkali metal, ammonium and alkanolammonium salts ofpolyphosphates (exemplified by the tripolyphosphates, pyrophosphates,and glassy polymeric meta-phosphates), phosphonates, phytic acid,silicates, carbonates (including bicarbonates and sesquicarbonates),sulphates, and aluminosilicates. However, non-phosphate builders arerequired in some locales. Importantly, the compositions herein functionsurprisingly well even in the presence of the so-called "weak" builders(as compared with phosphates) such as citrate, or in the so-called"underbuilt" situation that may occur with zeolite or layered silicatebuilders.

Examples of silicate builders are the alkali metal silicates,particularly those having a SiO₂ :Na₂ O ratio in the range 1.6:1 to3.2:1 and layered silicates, such as the layered sodium silicatesdescribed in U.S. Pat. No. 4,664,839, issued May 12, 1987 to H. P.Rieck. NaSKS-6 is the trademark for a crystalline layered silicatemarketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlikezeolite builders, the Na SKS-6 silicate builder does not containaluminum. NaSKS-6 has the delta-Na₂ SiO₅ morphology form of layeredsilicate. It can be prepared by methods such as those described inGerman DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly preferredlayered silicate for use herein, but other such layered silicates, suchas those having the general formula NaMSi_(x) O_(2x+1).yH₂ O wherein Mis sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and yis a number from 0 to 20, preferably 0 can be used herein. Various otherlayered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, asthe alpha, beta and gamma forms. As noted above, the delta-Na₂ SiO₅(NaSKS-6 form) is most preferred for use herein. Other silicates mayalso be useful such as for example magnesium silicate, which can serveas a crispening agent in granular formulations, as a stabilizing agentfor oxygen bleaches, and as a component of suds control systems.

Examples of carbonate builders are the alkaline earth and alkali metalcarbonates as disclosed in German Patent Application No. 2,321,001published on Nov. 15, 1973.

Aluminosilicate builders are useful in the present invention.Aluminosilicate builders are of great importance in most currentlymarketed heavy duty granular detergent compositions, and can also be asignificant builder ingredient in liquid detergent formulations.Aluminosilicate builders include those having the empirical formula:

    M.sub.z (zAlO.sub.2).sub.y !.xH.sub.2 O

wherein z and y are integers of at least 6, the molar ratio of z to y isin the range from 1.0 to about 0.5, and x is an integer from about 15 toabout 264.

Useful aluminosilicate ion exchange materials are commerciallyavailable. These aluminosilicates can be crystalline or amorphous instructure and can be naturally-occurring aluminosilicates orsynthetically derived. A method for producing aluminosilicate ionexchange materials is disclosed in U.S. Pat. No. 3,985,669, Krummel, etal, issued Oct. 12, 1976. Preferred synthetic crystallinealuminosilicate ion exchange materials useful herein are available underthe designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. Inan especially preferred embodiment, the crystalline aluminosilicate ionexchange material has the formula:

    Na.sub.12  (AlO.sub.2).sub.12 (SiO.sub.2).sub.12 !.xH.sub.2 O

wherein x is from about 20 to about 30, especially about 27. Thismaterial is known as Zeolite A. Dehydrated zeolites (x=0-10) may also beused herein. Preferably, the aluminosilicate has a particle size ofabout 0.1-10 microns in diameter.

Organic detergent builders suitable for the purposes of the presentinvention include, but are not restricted to, a wide variety ofpolycarboxylate compounds. As used herein, "polycarboxylate" refers tocompounds having a plurality of carboxylate groups, preferably at least3 carboxylates. Polycarboxylate builder can generally be added to thecomposition in acid form, but can also be added in the form of aneutralized salt. When utilized in salt form, alkali metals, such assodium, potassium, and lithium, or alkanolammonium salts are preferred.

Included among the polycarboxylate builders are a variety of categoriesof useful materials. One important category of polycarboxylate buildersencompasses the ether polycarboxylates, including oxydisuccinate, asdisclosed in Berg, U.S. Pat. No. 3,128,287, issued Apr. 7, 1964, andLamberti et al, U.S. Pat. No. 3,635,830, issued Jan. 18, 1972. See also"TMS/TDS" builders of U.S. Pat. No. 4,663,071, issued to Bush et al, onMay 5, 1987. Suitable ether polycarboxylates also include cycliccompounds, particularly alicyclic compounds, such as those described inU.S. Pat. Nos. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.

Other useful detergency builders include the etherhydroxypolycarboxylates, copolymers of maleic anhydride with ethylene orvinyl methyl ether, 1,3,5-trihydroxy benzene-2,4,6-trisulphonic acid,and carboxymethyloxysuccinic acid, the various alkali metal, ammoniumand substituted ammonium salts of polyacetic acids such asethylenediamine tetraacetic acid and nitrilotriacetic acid, as well aspolycarboxylates such as mellitic acid, succinic acid, oxydisuccinicacid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate builders, e.g., citric acid and soluble salts thereof(particularly sodium salt), are polycarboxylate builders of particularimportance for heavy duty liquid detergent formulations due to theiravailability from renewable resources and their biodegradability.Citrates can also be used in granular compositions, especially incombination with zeolite and/or layered silicate builders.Oxydisuccinates are also especially useful in such compositions andcombinations.

Also suitable in the detergent compositions of the present invention arethe 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compoundsdisclosed in U.S. Pat. No. 4,566,984, Bush, issued Jan. 28, 1986. Usefulsuccinic acid builders include the C₅ -C₂₀ alkyl and alkenyl succinicacids and salts thereof. A particularly preferred compound of this typeis dodecenylsuccinic acid. Specific examples of succinate buildersinclude: laurylsuccinate, myristylsuccinate, palmitylsuccinate,2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like.Laurylsuccinates are the preferred builders of this group, and aredescribed in European Patent Application 86200690.5/0,200,263, publishedNov. 5, 1986.

Other suitable polycarboxylates are disclosed in U.S. Pat. No.4,144,226, Crutchfield et al, issued Mar. 13, 1979 and in U.S. Pat. No.3,308,067, Diehl, issued Mar. 7, 1967. See also Diehl U.S. Pat. No.3,723,322.

Fatty acids, e.g., C₁₂ -C₁₈ monocarboxylic acids, can also beincorporated into the compositions alone, or in combination with theaforesaid builders, especially citrate and/or the succinate builders, toprovide additional builder activity. Such use of fatty acids willgenerally result in a diminution of sudsing, which should be taken intoaccount by the formulator.

In situations where phosphorus-based builders can be used, the variousalkali metal phosphates such as the well-known sodium tripolyphosphates,sodium pyrophosphate and sodium orthophosphate can be used. Phosphonatebuilders such as ethane-1-hydroxy-1,1-diphosphonate and other knownphosphonates (see, for example, U.S. Pat. Nos. 3,159,581; 3,213,030;3,422,021; 3,400,148 and 3,422,137) can also be used.

Polymeric soil release agents useful in the present invention alsoinclude cellulosic derivatives such as hydroxyether cellulosic polymers,copolymeric blocks of ethylene terephthalate or propylene terephthalatewith polyethylene oxide or polypropylene oxide terephthalate, and thelike. Such agents are commercially available and include hydroxyethersof cellulose such as METHOCEL (Dow). Cellulosic soil release agents foruse herein also include those selected from the group consisting of C₁-C₄ alkyl and C₄ hydroxyalkyl cellulose; see U.S. Pat. No. 4,000,093,issued Dec. 28, 1976 to Nicol, et al.

Soil release agents characterized by poly(vinyl ester) hydrophobesegments include graft copolymers of poly(vinyl ester), e.g., C₁ -C₆vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkyleneoxide backbones, such as polyethylene oxide backbones. See EuropeanPatent Application 0 219 048, published Apr. 22, 1987 by Kud, et al.Commercially available soil release agents of this kind include theSOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (WestGermany).

One type of preferred soil release agent is a copolymer having randomblocks of ethylene terephthalate and polyethylene oxide (PEO)terephthalate. The molecular weight of this polymeric soil release agentis in the range of from about 25,000 to about 55,000. See U.S. Pat. No.3,959,230 to Hays, issued May 25, 1976 and U.S. Pat. No. 3,893,929 toBasadur issued Jul. 8, 1975.

Another preferred polymeric soil release agent is a polyester withrepeat units of ethylene terephthalate units contains 10-15% by weightof ethylene terephthalate units together with 90-80% by weight ofpolyoxyethylene terephthalate units, derived from a polyoxyethyleneglycol of average molecular weight 300-5,000. Examples of this polymerinclude the commercially available material ZELCON 5126 (from Dupont)and MILEASE T (from ICI). See also U.S. Pat. No. 4,702,857, issued Oct.27, 1987 to Gosselink.

Another preferred polymeric soil release agent is a sulfonated productof a substantially linear ester oligomer comprised of an oligomericester backbone of terephthaloyl and oxyalkyleneoxy repeat units andterminal moieties covalently attached to the backbone. These soilrelease agents are described fully in U.S. Pat. No. 4,968,451, issuedNov. 6, 1990 to J. J. Scheibel and E. P. Gosselink. Other suitablepolymeric soil release agents include the terephthalate polyesters ofU.S. Pat. No. 4,711,730, issued Dec. 8, 1987 to Gosselink et al, theanionic end-capped oligomeric esters of U.S. Pat. No. 4,721,580, issuedJan. 26, 1988 to Gosselink, and the block polyester oligomeric compoundsof U.S. Pat. No. 4,702,857, issued Oct. 27, 1987 to Gosselink.

Preferred polymeric soil release agents also include the soil releaseagents of U.S. Pat. No. 4,877,896, issued Oct. 31, 1989 to Maldonado etal, which discloses anionic, especially sulfoaroyl, end-cappedterephthalate esters.

If utilized, soil release agents will generally comprise from about0.01% to about 10.0%, by weight, of the detergent compositions herein,typically from about 0.1% to about 5%, preferably from about 0.2% toabout 3.0%.

Chelating Agents--The detergent compositions herein may also optionallycontain one or more iron and/or manganese chelating agents. Suchchelating agents can be selected from the group consisting of aminocarboxylates, amino phosphonates, polyfunctionally-substituted aromaticchelating agents and mixtures therein, all as hereinafter defined.Without intending to be bound by theory, it is believed that the benefitof these materials is due in part to their exceptional ability to removeiron and manganese ions from washing solutions by formation of solublechelates.

Amino carboxylates useful as optional chelating agents includeethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates,nitrilotriacetates, ethylenediamine tetraproprionates,triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, andethanoldiglycines, alkali metal, ammonium, and substituted ammoniumsalts therein and mixtures therein.

Amino phosphonates are also suitable for use as chelating agents in thecompositions of the invention when at lease low levels of totalphosphorus are permitted in detergent compositions, and includeethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred,these amino phosphonates to not contain alkyl or alkenyl groups withmore than about 6 carbon atoms.

Polyfunctionally-substituted aromatic chelating agents are also usefulin the compositions herein. See U.S. Pat. No. 3,812,044, issued May 21,1974, to Connor et al. Preferred compounds of this type in acid form aredihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelator for use herein is ethylenediaminedisuccinate ("EDDS"), especially the S,S! isomer as described in U.S.Pat. No. 4,704,233, Nov. 3, 1987, to Hartman and Perkins.

If utilized, these chelating agents will generally comprise from about0.1% to about 10% by weight of the detergent compositions herein. Morepreferably, if utilized, the chelating agents will comprise from about0.1% to about 3.0% by weight of such compositions.

Polymeric Dispersing Agents--Polymeric dispersing agents canadvantageously be utilized at levels from about 0.1% to about 7%, byweight, in the compositions herein, especially in the presence ofzeolite and/or layered silicate builders. Suitable polymeric dispersingagents include polymeric polycarboxylates and polyethylene glycols,although others known in the art can also be used. It is believed,though it is not intended to be limited by theory, that polymericdispersing agents enhance overall detergent builder performance, whenused in combination with other builders (including lower molecularweight polycarboxylates) by crystal growth inhibition, particulate soilrelease peptization, and anti-redeposition.

Polymeric polycarboxylate materials can be prepared by polymerizing orcopolymerizing suitable unsaturated monomers, preferably in their acidform. Unsaturated monomeric acids that can be polymerized to formsuitable polymeric polycarboxylates include acrylic acid, maleic acid(or maleic anhydride), fumaric acid, itaconic acid, aconitic acid,mesaconic acid, citraconic acid and methylenemalonic acid. The presencein the polymeric polycarboxylates herein or monomeric segments,containing no carboxylate radicals such as vinylmethyl ether, styrene,ethylene, etc. is suitable provided that such segments do not constitutemore than about 40% by weight.

Particularly suitable polymeric polycarboxylates can be derived fromacrylic acid. Such acrylic acid-based polymers which are useful hereinare the water-soluble salts of polymerized acrylic acid. The averagemolecular weight of such polymers in the acid form preferably rangesfrom about 2,000 to 10,000, more preferably from about 4,000 to 7,000and most preferably from about 4,000 to 5,000. Water-soluble salts ofsuch acrylic acid polymers can include, for example, the alkali metal,ammonium and substituted ammonium salts. Soluble polymers of this typeare known materials. Use of polyacrylates of this type in detergentcompositions has been disclosed, for example, in Diehl, U.S. Pat. No.3,308,067, issued Mar. 7, 1967.

Acrylic/maleic-based copolymers may also be used as a preferredcomponent of the dispersing/anti-redeposition agent. Such materialsinclude the water-soluble salts of copolymers of acrylic acid and maleicacid. The average molecular weight of such copolymers in the acid formpreferably ranges from about 2,000 to 100,000, more preferably fromabout 5,000 to 75,000, most preferably from about 7,000 to 65,000. Theratio of acrylate to maleate segments in such copolymers will generallyrange from about 30:1 to about 1:1, more preferably from about 10:1 to2:1. Water-soluble salts of such acrylic acid/maleic acid copolymers caninclude, for example, the alkali metal, ammonium and substitutedammonium salts. Soluble acrylate/maleate copolymers of this type areknown materials which are described in European Patent Application No.66915, published Dec. 15, 1982, as well as in EP 193,360, published Sep.3, 1986, which also describes such polymers comprisinghydroxypropylacrylate. Still other useful dispersing agents include themaleic/acrylic/vinyl alcohol terpolymers. Such materials are alsodisclosed in EP 193,360, including, for example, the 45/45/10 terpolymerof acrylic/maleic/vinyl alcohol.

Another polymeric material which can be included is polyethylene glycol(PEG). PEG can exhibit dispersing agent performance as well as act as aclay soil removal-antiredeposition agent. Typical molecular weightranges for these purposes range from about 500 to about 100,000,preferably from about 1,000 to about 50,000, more preferably from about1,500 to about 10,000.

Polyaspartate and polyglutamate dispersing agents may also be used,especially in conjunction with zeolite builders. Dispersing agents suchas polyaspartate preferably have a molecular weight (avg.) of about10,000.

Brightener--Any optical brighteners or other brightening or whiteningagents known in the art can be incorporated at levels typically fromabout 0.01% to about 1.2%, by weight, into the detergent compositionsherein. Commercial optical brighteners which may be useful in thepresent invention can be classified into subgroups, which include, butare not necessarily limited to, derivatives of stilbene, pyrazoline,coumarin, carboxylic acid, methinecyanines,dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered-ringheterocycles, and other miscellaneous agents. Examples of suchbrighteners are disclosed in "The Production and Application ofFluorescent Brightening Agents", M. Zahradnik, Published by John Wiley &Sons, New York (1982).

Suds Suppressors--Compounds for reducing or suppressing the formation ofsuds can be incorporated into the compositions of the present invention.Suds suppression can be of particular importance in the so-called "highconcentration cleaning process" and in front-loading European-stylewashing machines.

A wide variety of materials may be used as suds suppressors, and sudssuppressors are well known to those skilled in the art. See, forexample, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition,Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category ofsuds suppressor of particular interest encompasses monocarboxylic fattyacid and soluble salts therein. See U.S. Pat. No. 2,954,347, issued Sep.27, 1960 to Wayne St. John. The monocarboxylic fatty acids and saltsthereof used as suds suppressor typically have hydrocarbyl chains of 10to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitablesalts include the alkali metal salts such as sodium, potassium, andlithium salts, and ammonium and alkanolammonium salts.

The detergent compositions herein may also contain non-surfactant sudssuppressors. These include, for example: high molecular weighthydrocarbons such as paraffin, fatty acid esters (e.g., fatty acidtriglycerides), fatty acid esters of monovalent alcohols, aliphatic C₁₈-C₄₀ ketones (e.g., stearone), etc.

Another preferred category of non-surfactant suds suppressors comprisessilicone suds suppressors. This category includes the use ofpolyorganosiloxane oils, such as polydimethylsiloxane, dispersions oremulsions of polyorganosiloxane oils or resins, and combinations ofpolyorganosiloxane with silica particles wherein the polyorganosiloxaneis chemisorbed or fused onto the silica. Silicone suds suppressors arewell known in the art and are, for example, disclosed in U.S. Pat. No.4,265,779, issued May 5, 1981 to Gandolfo et al and European PatentApplication No. 89307851.9, published Feb. 7, 1990, by Starch, M. S.

Dye Transfer Inhibiting Agents--The compositions of the presentinvention may also include one or more materials effective forinhibiting the transfer of dyes from one fabric to another during thecleaning process. Generally, such dye transfer inhibiting agents includepolyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymersof N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine,peroxidases, and mixtures thereof. If used, these agents typicallycomprise from about 0.01% to about 10% by weight of the composition,preferably from about 0.01% to about 5%, and more preferably from about0.05% to about 2%.

Further Processing

The "pastilles" or "micropastilles" may be dusted with a fine powder inorder to improve their flow properties. Suitable powders are crystallineor amorphous aluminosilicates, especially Zeolite A; crystalline oramorphous silica, clay, talc.

Finally the finished "pastilles" or "micropastilles" are preferablycombined with other commonly used detergent components to form afinished detergent composition. Other detergent components includedetergent builders, enzymes, bleach, such perborate or percarbonate,bleach activators, polymeric soil release agents, chelating agents, claysoil removal agents, polymeric dispersing agents, suds suppressingagents, optical brightener, perfume (such as those described in detailon pages 19 to 45 of WO92/06160).

EXAMPLES

C16-C18 N-methyl glucamide (NMG) is synthesised with ethoxylatednonionic surfactant (average of 5 moles of ethylene oxide per mole ofC12-C14 alcohol, AE5) present during the reaction of methyl ester andN-methyl glucamine as described in WO92/06160. The nonionic surfactantacts as a melting point depressor which allows the reaction to be runwithout forming cyclic glucose amides which are undesirable. Thesurfactant mixture obtained is then mixed with other detergentcomponents.

The resulting surfactant paste had the following composition:

    ______________________________________                    Ex. 1  Ex. 2    Ex. 3                                         Ex. 4                    wt %   wt %     wt % wt %    ______________________________________    Ethoxylated nonionic                    20     30       27   15    surfactant (AE5)    C12-C14 N-methyl                    47     35       63   --    glucamide (12-14NMG)    C16-C18 N-methyl                    --     35       --   35    glucamide (16-18NMG)    C12-C16 alkyl   33     --       --   --    sulphate (AS),    100% active powder    C12-C16 alkyl   --     --       --   50    sulphate (AS), 80%    active aqueous paste    Hydrogenated Fatty                    --     --       10   --    Acid (Hyfac)    ______________________________________                    Ex. 6  Ex. 7    Ex. 8                                         Ex. 9                    wt %   wt %     wt % wt %    ______________________________________    Ethoxylated nonionic                    30     20       25   10    surfactant (AE5)    Alkyl polyglycoside                    70     --       --   80    C12-C14 N-methyl                    --     47       55   --    glucamide (12-14NMG)    Secondary alkyl --     33       --   --    sulphate    (SAS)    Anionic surfactant                    --     --       20   --    C12-C16 alkyl   --     --       --   10    sulphate (AS), 80%    active aqueous paste    ______________________________________

The anionic surfactant in example 9 is selected alternatively fromC13-15 alkyl sulphate (with an average of 6 ethoxy groups per molecule),AE6S; oleoyl sarcosinate; alkyl glycoside, LAS, or methyl estersulphate. The anionic surfactant of example 9 was also replaceable bycationic surfactant; and with a 50:50 mix of cationic surfactant withLAS.

    ______________________________________               Ex. 10  Ex. 11  Ex. 12    Ex. 13               wt %    wt %    wt %      wt %    ______________________________________    Ethoxylated  60        25      25      15    nonionic surfactant    (AE5)    C12-C14 N-methyl                 --        55      55      35    glucamide (12-    14NMG)    C12-C16 alkyl                 20        --      --      10    sulphate (AS), 80%    active aqueous    paste    Polymer      20        20      10       7    Detergent powder                 --        --      10      15    Hydrogenated Fatty                 --        --      --      10    Acid (Hyfac)    Minors       --        --      --       8    ______________________________________

In examples 10 to 13, the polymer used is alternately PVP, PVNO, PVPVI,polyaspartic acid, terpolymer, acrylic-maleic copolymer, soil releasepolymer, polyethylene glycol or polyethylene oxide.

The detergent powder of example 12 and 13 is alternately silica,zeolite, amorphous silicate, crystalline silicate, smectite clay,carbonate, bicarbonate, citrate or citric acid.

The minors of example 13 are detergent enzymes (5 parts), perfume (1part), brightener (1 part), together with 1 part of either phosphonateor EDDS.

    ______________________________________               Ex. 14 Ex. 15   Ex. 16   Ex. 17               wt %   wt %     wt %     wt %    ______________________________________    Ethoxylated nonionic                 20       20       20     20    surfactant (AE5)    C12-C14 N-methyl                 40       40       40     40    glucamide (12-14NMG)    C12-C16 alkyl                 10       10       10     10    sulphate (AS), 80%    active aqueous paste    Polymer       3        3        3      3    Silicate     --       --       --      5    Sodium carbonate                  5       10       10      5    Sodium perborate                 10       --       10     --    Sodium percarbonate                 --       10       --     10    Tetraacetyl ethylene                  5        5        5      5    diamine    (TAED)    Minors        7        2        2      2    ______________________________________

In examples 14 to 17, the polymer used are alternately PVP, PVNO, PVPVI,polyaspartic acid, terpolymer, acrylic-maleic copolymer, soil releasepolymer, polyethylene glycol or polyethylene oxide.

The minors of example 14 are detergent enzymes (5 parts), perfume (1part), phosphonate (1 part); the minors of examples 15 to 17 are 1 partof phosphonate and 1 part of EDDS.

The silicate of example 17 is either crystalline or amorphous silicate.

    ______________________________________               Ex. 18 Ex. 19   Ex. 20   Ex. 21               wt %   wt %     wt %     wt %    ______________________________________    Ethoxylated nonionic                 20       25       20     20    surfactant (AE5)    C12-C14 N-methyl                 50       50       50     50    glucamide (12-14NMG)    C12-C16 alkyl                 10       15       15     15    sulphate (AS), 80%    active aqueous paste    Tetraacetyl ethylene                 20       --       --     --    diamine    (TAED)    Minors       --       10       --     --    Polyaspartic acid                 --       --       15     --    Chelant      --       --       --     15    ______________________________________

The minors of example 19 are alternately detergent enzymes, brightenersor perfume.

The chelant of example 21 is either phosphonate or ethylene diaminedisuccinate (EDDS).

In any of Examples 1 to 21, the AE5 can be replaced with, for example,ethoxylated nonionic surfactant having an average of 3 moles of ethyleneoxide per mole of C12-C15 alcohol, AE3; or with nonionic surfactanthaving an average of 7 moles of ethylene oxide per mole of C13-C15alcohol, AE7.

In any of Examples 1 to 3, 7, 8 and 11 to 21, the C12-14 NMG can bereplaced with, for example, C16-18 NMG; or by C16-18 N-butylglucamide.

    ______________________________________                 Ex. 22   Ex. 23   Ex. 24 Ex. 25                 wt %     wt %     wt %   wt %    ______________________________________    Ethoxylated nonionic                 21.6     16.8     21.6   16.8    surfactant (AE5)    C12-C14 N-methyl                 50.4     39.2     50.4   39.2    glucamide (12-14NMG)    fatty acid   18       14       18     14    Sodium sulphate                 10       30    Citric acid                    10     30    ______________________________________                 Ex. 26      Ex. 27  Ex. 28                 wt %        wt %    wt %    ______________________________________    Ethoxylated nonionic                 24          21      24    surfactant (AE5)    C12-C14 N-methyl                 56          49      56    glucamide (12-14NMG)    fatty acid               30      20    Sodium carbonate                 20    ______________________________________

Paste compositions are prepared according to the Examples 1 to 28 bymixing the components. In each example, the paste is then pumped to aRotoform® manufactured by Sandvik Conveyor GmbH. Using this equipmentdrops of surfactant paste are formed on a stainless steel conveyor belt,each drop having a diameter of approximately 1 mm. The underside of theconveyor belt is cooled by spraying on a chilled water/glycol mixture.The solidified pastilles are then removed from the belt and dusted withfrom 2 to 5 parts by weight of Zeolite A in a drum mixer.

In all of these examples the bulk density of the finished pastillatedcomposition is about 450 g/l.

What is claimed is:
 1. A process for the manufacture of detergentcompositions from a surfactant paste which is substantially in the solidphase at temperatures of 25° C. and below comprising the steps of:(i)mixing the surfactant paste at a temperature above its softening point,the surfactant paste consisting essentially of at least 50% by weight ofnonionic surfactant and an anionic surfactant selected from the groupconsisting of alkyl benzene sulfonates, alkyl sulfates, alkyl alkoxysulfates, alkyl alkoxy carboxylates, sulfated polyglycosides and oleylsarcosinates, wherein the weight ratio of the anionic surfactant to thenonionic surfactant is from 1:100 to 1:1; (ii) forming the moltensurfactant paste into drops on a cooling surface; (iii) forming solidpastilles by cooling the drops of molten surfactant paste; and (iv)removing solidified pastilles from the cooling surface.
 2. A processaccording to claim 1 wherein the surfactant paste has a water componentof less than 15% by weight of the surfactant paste.
 3. A processaccording to claim 2 wherein the surfactant paste has a water componentof less than 10% by weight of the surfactant paste.
 4. A processaccording to claim 1 wherein said nonionic surfactants are selected fromthe group consisting of ethoxylated nonionic surfactants, glycerolethers, glucosamides, glycerol amides, glycerol esters, fatty acidesters, fatty amides, alkyl polyglycosides, alkyl polyglycol ethers,ethoxylated alkyl phenols and mixtures thereof.
 5. A process accordingto claim 4 wherein said nonionic surfactant is a mixture of polyhydroxyfatty acid amide and an ethoxylated nonionic surfactant in a weightratio of from 3:7 to 7:3.
 6. A process according to claim 1 wherein thesurfactant paste further consists essentially of other non-surfactantdetergent ingredients selected from the group consisting of polymericand oligomeric materials and mixtures thereof.
 7. A process according toclaim 6 wherein the polymeric materials are selected from the groupconsisting of polymeric carboxylates, polyethylene glycols,polyaspartates, polyglutamates, and mixtures thereof.
 8. A processaccording to claim 1 wherein the molten surfactant paste is formed intodrops by a continuous rotary drop former comprising outer and innercoaxial cylinders, both cylinders comprising a series of openings, atleast one of the cylinders being rotatable.
 9. A process according toclaim 8 wherein the molten surfactant drops are formed on a continuoussteel cooling belt.
 10. A process according to claim 9 wherein themolten surfactant drops are cooled by spraying a cooling liquid on tothe opposite side of the belt to the side on which the drops are formed.